Substitution products of the carbazole sulphonic acids



" sodium chloride.

Patented Sept. 11, I934 :17;

UNITED STATES PATENT- ()ICE SUBSTITU' IION PRODUCTS OF THE CARBAZOLESULPHONIO ACIDS Friedrich Muth and Albert Sclimelzer, Elberfeld,

Germany, assignors to General Aniline Works, Inc., New York, N. Y., acorporation of Dela ware No Drawing. Application January 7, 1930, SerialNo. 419,197. In Germany January 23, 19219 7 Claims. (01. 26046) (soul).A,

wherein A stands for an anion other than -SO:H and x stands for one ofthe numbers 1, 2 and 3, the positions 1 and 8 being not both substitutedby OI-I-groups simultaneously with the substitution of both the 3 and 6positions by SO3H-groups.

The new acids form in the free state colorless or weakly coloredcrystals which dissolve readily in water. They are valuable intermediateproducts for the preparation of dyestuffs and pharmaceutical products.

Our invention is illustrated by the following examples, without beinglimited thereto; the parts being by weight:

Erample 1.1 -hydrzcg1-carbaeole 3.6.8 trisul phonic-acid 100 parts ofl-amino-carbazole3.6.8-trisulphonic acid (acid sodium salt) aredissolved in 200 parts of hot water and diazotized after adding 180parts of 25% sulphuric acid at a temperature of about 35-40 C. The diazocompound thus formed is separated as a yellow paste of crystals; theseparation is completed by salting out with The separated diazo compoundis dissolved in 5000 parts of hot water; this solution is dropped whilestirring within two hours into a strongly boiling solution of 50 partsof crystallized copper sulphate in- 2000 parts of water. To thissolution 250 parts of diluted sulphuric acid are added. A vividdevelopment of nitrogentakes place. The finish of the reaction isdetermined by taking out a sample and testing whether it still couplesto form a dyestufi on the addition of an azo component. After thereaction is' complete, the solution is made alkaline by means of sodiumcarbonate and filtered off with suction from'the precipitated coppercarbonate. By concentrating the solutionthehydroxy-carbazole-3.6.8-trisulphonic acid separates in long, 6!weakly brown-colored needles. 'In an analogous manner the followingcompounds are obtained: 1-hydroxy-carbazole12.6.8-trisulphonic acid, 1-hydroxy carbazole 4.6.8 trisulphonic acid, 1- hydroxycarbazole3.6-disulphonic acid, 1 hydroxy-carbazole-3-sulphonic acid, andl-hydroxycarbazole-G-sulphonic acid.

Example 2.2 hydrory carbazo'le 3.6.8-trisulphonic-acid 7.0

100 parts of 2-amino-carbazole-3.6.8-trisulphonic acid are dissolved inabout 2000 parts of water and 100 parts of diluted sulphuric acid anddiazotized at room temperature by dropping in a solution of sodiumnitrite. By salting out, the diazo compound is separated in yellowneedles, often grouped in starlets. The separated diazo compound isdissolved in about 1500 parts of water and dropped into a boilingdiluted sulphuric acid containing 250 parts of sulphuric acid in 500parts of water with the addition of a small quantity of copper powder;The decomposition is performed very quickly with the development ofnitrogen. The solution freed from copper is concentrated and theZ-hydroxy-car- 8 5 bazole -trisulphonic acid is then salted out. In thisway it is obtained in the form of short, spindle-shaped needles. In ananalogous manner the following compounds are obtained: 2-hydroxy-carbazole-l.6.8-trisulphonic acid,2-hydroxy-carbazole-1.4.8-trisulphonic acid,2-hydroxy-carbazole-3.G-disulphonic acid, and2-hydroxy-carbazole-fisulphonic acid.

Example 3.-3 hydrory carbazole 1.6.8-trisulphonic acidbazole-1.5.8-trisulphonic acid, E-hydroxy-car-'bazole-1.5.7-trisulphonic acid, 3-hydroxy-carbazole-2.6.8-trisulphonicacid, B-hydrOXy-carbazole.-2.5.7-trisulphonic acid, 3-hydroxy-car- .110

the stEam-bath for some hours. I violet solution is filtered from atrifle of black bazole-G.8-disu1phonic acid, 3-hydr0Xy-carbazole5.7-disulphonic acid, 3-hydroxy-carbazole-6-sulphonic acid, and3-hydroxy-carbazole-8-sulphonic acid.

Example I 4.1.8-dihydroxy-carbaeole 3.G-disulphonic acid 100 parts of1-amino-8-hydroxy-carbazole3.6-

disulphonic acid are diazotized and boiled as mentioned in Example 1.The 1.8-dihydroxycarbazo1e-3.6-disulphonic acid obtained thereby isidentical with the acid described in German Patent 224,952.

In an analogous manner the following compounds are obtained:2.7-dihydroxy-carb'azole- 3.6-disulphonic acid,3.6-dihydroXy-carbaz0le-1.8- disulphonic acid,2.7-dihydroXy-carbazole-S-sulphonic acid, and3.6-dihydroxy-carbazole-l-sulphonic acid.

Example 5.-1Jig/dressy-8-iodo-carbazoZc-3fi-disulphonic acid v 100 partsof 1-hydroxy-8-amino-carbazole-3.6- disulphonio acid are suspended in100 parts .of water and made Congo-acid by the addition of about 100parts of diluted sulphonic acid orhydrochloric acid. At a temperature of60-70 C a solution of 10% sodium nitrite is dropped in until thediazotation is completed. "The diazo compound separates during theoperation in the form of solid needles. The separation is completed bysalting outthe cooled diazo solution. The isolated diazo-compound issuspended in about 500 parts of water'and after the addition of 60 partsof potassium iodide it is decomposed as quickly as possible by means ofcopper powder at the temperature of 85-90 C., Dissolution of thesuspended compound takes place, nitrogen being developed; from thefiltered hot solution than a small quantity ofhydroxy-carbazole-sulphonic acid crystallizes out in white needles.These are filtered off after cooling and the solution, freed fromcopper, is then carefully concentrated in vacuo. The acid isprecipitated in the form of weakly grey flakes by the addition ofalcohol; For further purifying, the acid is redissolved from dilutedalcohol.

The following compounds are obtained in an analogous manner:2-hydroxy-8-iodo-carbazole- 3.6-disulphonic acid, 3 hydroxy l iodo carbazole-6.8-disulphonic acid, 2-hydroxy-8-iod0- oarbazole-3.7-disulphonicacid, and l-hydroxy- 3.6-diiodc-carbazole-8-sulphonic acid.

Example 6.-1.Z' dicarbaeole disulphide .3 6.6-8.8-hexasalphonic acid'xanthogenic acid ester is suspended withabout 700 parts of water andheated to a temperature of '20-'75" C., while stirring; at a temperatureof "about 30 C. the development of nitrogen begins.

After the reaction is complete, parts of potassium hydroxide are addedthereto and heated on The. reddishdecomposition products and evaporatedon-the water bath to about 750 parts by volume. By

-sulphuric acid. and 50 parts of zinc dust.

trate' by means or sodium chloride.

acidifying with glacial acetic acid and adding sodium chloride thedisulphide-dicarbazole-hexasulphonic acid separates on cooling. Itcrystallizes from water in the ,formqof yellow, broad long'needles v vExample 7 .1 -mercapto-carbazoZe-3.6.8-trisalphonic acid 100 parts of1.1-dicarbazole-disulphide3.3- 6.6 8.8-hexasulphonic acid (preparedaccording to lilxarnpl'efi)- are dissolved in 1200 parts of water andboiled on .a reflux condenser for two hours after the addition of 150parts of 25% 7 After filtering with suction and cooling, the newcompound is salted out from the nearly colorless fil- The zinc salt ofthe 1 mercapto-carbazole-3.6.8trisulphonic acid is separated as a thickcrystal paste. The zinc salt is obtained in the form of long whiteneedles by recrystallizing it from water.

In an analogous manner, the following compounds are obtainedin the formof their. zinc salts: .2-mercapto carbazole3.6.8 trisulphonic acid, 3mercapto-carbazole 1.6.8-trisulphonic acid,.2-mercapto-carbazole-6.S-disulphonic acid, 1-mercaptocarbazole-3esulphonic acid, and 1-- meroapto-carbazole-S-sulphonic'acid.

Example 8.-1 chloro-carbazole 3.6.8 -'t1"isul'- phonic acid 100 parts of1-alIlinO-C2llb'dZGlE-3.6.8-l3llSlll-* phonic acid '(acid sodium salt)are dissolved in 2900 parts of hot water-after the addition of 260 partsof diluted hydrochloric acid and diazotized With 126 partsiby volume ofa 10% solution of sodium nitrite while cooling with ice. The diazocompound separated according to Example 1 is suspended, while beingstill moist, with about 500 parts by volume of diluted hydrochloric acidand at a temperature of about 30 C. brought into a solution of cuprouschloride which is prepared from 50 parts of crystallized coppersulphate, 50 parts of sodium chloride and 200-parts by volume of dilutedhydrochloric acid. Finally the mixture is heated until no more nitrogendevelops to a temperature of about 60-70-C.- The new acid separates as awhite thick paste; it is redissolved by the addition of a small amountof "Water.- After precipitation of the copper by 'means of hydrogensulphide, the solution of the acid is concentrated onthe water bathuntil crystallization begins. The l chloro --carbazole-3.6;8-trisulphonic acid crystallizes after cooling in form of finefibrous needles arranged in form of sheaves; the'acid is recrystallizedfrom alcohol of 40% strength. The following compounds are obtained in ananalogous manner: l-chlor0-carbazole- 2.6.8-trisulphonic acid,l-chloro-carbazole-dfi.8-

Example 9.2-chZom-carbazo2c-trisalphonic acid The diaz'o compound whichis obtained'and separated in a manner analogous to Example 2, issuspended in500' parts by volume of diluted hydrochloric acid and addedat room temperature to a solution of 50 parts of cuprous chloride,"dissolved in' 250 parts by-volume of a concentrated as described inExample 1.

hydrochloric acid. A thick redbr'own colored precipitate results whichis dissolved'especially on heating to a temperature of about -50" C.,nitrogen being developed; after cooling the acid crystallizes out fromthe clear, weakly olive c01- ored solution in form of long hair-likeneedles. This solution is diluted with water to about 600 parts byvolume and freed from copper by means of hydrogen sulphide. Afterconcentrating to about one third of the volume, the new acidcrystaliizes out from the filtrate in the form of long colorlessneedles. It has probably the constitution of a2-chloro-carbazole-3.6.8-trisulphonic acid. The following compounds areobtained in an analogous manner: 2-chloro-carbazole-1.6.8- trisulphonicacid, 2-chloro-carbazole-1.4.8-trisulphonic acid, 2-chloro carbazole 3.6disulphonic acid, 2chloro-carbazole-fi-sulphonic acid, andZ-chloro-carbazole-E.6.8-trisulphonic' acid.

Example 10.1 bromo carbazole 3.6.8 -trisuZ- phonic acid Thecarbazole-3.6.8-trisulphonic acid-l-diazonium-bromide obtained froml-amino-carbazole-3.6.8-trisulphonic acid in a manner analogous toExample 9,, is decomposed and worked up in the same way with a solutionof cuprous bromide. The new acid crystallizes in form of colorlessneedles. t separates from the aqueous solution by salting out in agel-like form.

The following compounds are obtained in an analogous manner:2-bromo-carbazole-1.6.8-tri sulphonic acid, 3-bromo-carbazole-1.5.7trisulphonic acid, 3 bromo carbazole 2.3.8 trisulphonic acid,3-bromo-carbazole-2.5.7 trisulphonic acid,3-bromo-carbazole-6.B-disulphonic acid, 3-bromo-carbazole-5.7-disulphonic acid, 3-bromocarbazole-6-sulphonic acid,3'-bromo-carbazole+ s-sulphonic acid, 2-hydroxy-8-bromo-carbazole-3.6-disulphonic acid, 3-hydroXy-1-bromo-carba zole-6.8-disulphonic acid,2-hydroxy-8-bromocarbazole-3.7-disulphonic acid, and l-hydroxy-3.6-dibromo-carbazole-8-sulphonic acid.

Example 11 .1 -iodo-carbazoZc-3.6.8-trisulphonic acid 100 parts of1-amino-carbazole-3.6.8-trisu1- phonic acid (acid potassium salt) "aredissolved in 2000 parts of water and 100 parts by volume of a 25%sulphuric acid and diazotized according to Example 1. The diazo solutionis poured into a solution of 90 parts of potassium iodide dissolved in160 parts of diluted sulphuric acid and parts of water, which is kept onthe boiling water bath. After all nitrogen has developed the teredsolution is concentrated to a very small amount. The 1 iodo carbazole3.6.8 trisulphonic acid is crystallized out in the form of solidyellowish-colored needles which are arranged in a star-like form. Byrecrystallizingfrom diluted alcohol, particularly in thepresence of asmall amount of bisulphite solution, the acid is obtained in form ofcolorless needles.

The following compounds are obtained in an analogous manner:2.7-diiodo-carbazole-3.6-disulphonic acid,3.6-diiodo-carbazole-1.8-disu1- phonic acid, 2.7diiodo-carbazole-8-monosu1- phonic acid, and3.6-diiodo-carbazole-l-monosulphonic acid.

Example 1 2 .-1 -cyanogen-carbazole-3.6.8-t1'isulphonic acid 100 partsof 1-amino-carbazo1e-3.6;8-trisulphonic acid (acid potassium salt) arediazotized The diazo solutionis poured at a temp'era'ture of --70" G.into an aqueous solution of a potassium cupricyanide which is preparedby adding an aqueous solution of 28 parts of crystallized coppersulphate to an aqueous solution of 29 parts of 100% potassium cyanideand lfi-partsof 23.3% of ammonia. The diazo compound decomposes:immediately, nitrogen being developed. Finally it is boiledfor 30minutes and then allowed to cool; the filtered solution is saltedoutbymeans of sodium chloride. The I-cydriogen-carbazole-B.6.8-trisulphonicacid separates in the form of a thick paste of brownish-coloredcrystals. By recrystallizing from water in thepresence of a small amountof animal charcoal it is obtained-in the form of weakly yellow colored,long broad needles.

-The'following compounds are obtained in an analogous manner and possesssimilar properties: 2-cyanogen-carbazole-l.6.3-trisulphonic acid, 2-cyanog'en-carbazole-l. i.8 trisulphonic acid, 2Cyanogen-carbazole-B;6-disulphonic acid,Z-cyanogen-carbazole-S-sulphonic acid, 2-cyanogencarbazole".6.8-trisu1phonic acid, 1-cyancgen-8- hydrOXy-caibaZoIe-B.6-disulphonicacid, and 1- cyanogen 8 chioro carbazole 3.6-disulphonic acid. 7

Example 13. 3-cyanogen-carbazoZe-1.5.8-trisulphonic acid According toExample 3, 106 parts of 3-aminocarbazole-l.6.8-trisulphonic acid arediazotized and transformed into the 3-cyanogen-carbazole-1.6.8-trisulphonic acid as described in Example 12. The acid is obtainedin the form of yellowcolored, broad needles by recrystallizing fromwater in the presence of a small amount of animal charcoal. I

1 The following compounds are obtained in an analogous manner:3.-cyanogenoarbazole-1.5.8- trisulphonic acid,3cyanogen-earbazole-l.537- trisulphonic acid, 3cyanogen-carbazole-2.3.8-trisulphonic acid, 3-cyanogen-carbazole-2.5.7- trisulphonic acid,3-cyanogen-carbazole-6.S-disulphonic acid, 3-cyanogen-carbazole5.7-disulphonic acid, v 3-cyanogen-carbazole-8-hydroxy- 1.6-disulphonic acid,B-cyanogen-carbazole-fisulphonic acid, and 3cyanogen-carbazole-8-sulphonic acid. When using instead of cuprous cyanide, cuprous tliiocyanidein an analogous mannet, the corresponding thiocyanides of'carbazolesulphonic acids are produced, for example, 1- thiocyanogencarbazole-3.6.8-trisu1phonic acid.

Example 14.1-hydraeino-cdrbazole-3.6.8-trisul phonic acid arates bysalting out with sodium chloride. It is then finely suspended in 400parts by volume of concentrated hydrochloric acid. A solution of 200parts of stannous chloride in 150 parts of concentrated hydrochloricacid, which is cooled to a-temperature of 0 C.,'is added at atemperature of- 0 C.,- while stirring. The diazo compound dissolvesimmediately. Within a short time the hydrazine begins to separate asayvoluminous mass. After several hours the white crystalpasteis suckedoff. It is purified by dissolving in about 3000 parts'of water of 50? C.and filtering; f-The nearly colorless filtrate is salt.- ed out withabout 400 parts of sodium chloride.

The l hydrazino-carbazole-3.6.8 trisulphonic acid is crystallized fromavery dilute solution Example 15.Z hydrazine carbdzole' e trisul Qphonic acid 100 parts of 2-amino-carbazole-trisulphonio acid arediazotized in a manner analogous. to Example 9 and thediazonium chlorideis separated-The diazo compound is stirred with about 800 parts byvolume of concentrated hydrochloric acid to a paste and dropped at atemperature or" 0 G. into a solution of stannous chloride prepared from200 parts of crystallized stannous chloride and 160 parts by volume ofconcentrated hydrochloric acid. X

The diazo compound dissolves, and 'a thick white precipitate separates,after standing at room temperature for about one day. It is then suckedofi and Washed first with concentrated, then with diluted hydrochloricacid. Further purification is accomplished by dissolving in warm Waterand by the addition'of sodium chloride. After cooling the new acidcrystallizes out in colorless needles. In an analogous manner thefollowing compounds are obtainable:2-hydrazino-carbazole-SBB-trisulphonic acid,2-hydrazino-carbazole-1.6.S-trisulphonic acid,2-hydrazino-carbazole-l.4:.8trisu1phonic acid,2-hydrazino-carbazole3.G-disulphonic acid, and 2-hydrazino-carbazole-6'sulphonic acid.

Example 16.CarbazoZe-3.6.8-trisulphonic acid- Z-arsonic acid 100 partsof 1-amino-carbazo1e3 .6.8-trisulphonic acid are diazotized as describedin Example 8, and the diazo compound is separated by Jodium chloride. Itis stirred to form a paste with about 100 parts of water and neutralizedwith a 5 normal solution of potassium hydroxide at room temperature. Thediazo compound is quickly dissolved. From this solution it crystallizesand solidifies in form of a dark red paste. At room temperature, thecalculated quantity of a 5 normal solution of potassium arsenite isadded thereto. Nitrogen develops immediately. The development ofnitrogen being finished, the mixture is allowed to stand for about oneday, and then it is filtered off from a small quantity of anacid'crystallized in form of fine needles. The filtrate is carefullyconcentrated until crystallization begins. The arsonic acid is thusobtained in the form of a crystalline mass. It is purified byrecrystillization from a small amount of water. 1

In an analogous manner, the followingv compounds are obtained:carbazole-3.6-disulphonic acid-1.8-diarsonic acid,carbazole-3.6-disulphonic acid-l-hydroxy-Ei-arsonic acid,carbazole--3.6-disulphonic acid-1-arsonic acid, and carbazole-B-sulphonic acid-6arsonic acid.

Example 1 7 .--C'arbaeoZe-2 .6.8-trisulphonic-1 stibmic'acid 100 partsof lamino carbazole trisulphonic acid are dissolved in 2500 parts ofwater and. 60 parts by volume of diluted hydrochloric acid, anddiazotized by dropping in about 107 parts by volume of a 10% solution ofsodium nitrite. A solu tion of 24 parts of antimony oxide, dissolved inpar-ts by volume of pure concentrated hydrochloric acid, is added tothis diazo solution at a temperature of about 30 C. A thick precipitateresults immediately, which is dissolved by the additionof a 20% causticsoda lye. The yellow solution begins to froth strongly, while developing nitrogen. It is then heated to a temperature of 6070 C. and stirredfor about a quarter of 'anhour. After 1 hour the brown remainder issuckedofl? and the filtrate is concentrated until the crystallization.begins. The stibinic acid is separated as a weakly yellow-coloredcrystalline mass and further-purified by redissolving it from a smallamount of water.

In an analogous manner, the following compounds are obtained:carbazole-3.G-disulphonic- 1.8-distibinic acid,carbazole-3.fi-disulphonic-lhydroxy-8-stibinic acid, carbazole 3.6disulphonic-l-stibinic acid, and carbazole-3-sulphonic-6-stib'inio'acid;

We claim:

1. As new products, substitution products of carbazole sulphonic acidsofthe formula:

whereinA stands for an anion of the group consisting of the hydroxy,halo, cyano,.thio-cyano, mercapto, disulphide, hydrazino, arsonic acidand stibinic acid group, at the most two'of these anions being the sameones, and 3: stands for one of the numbers 1, 2 and 3, the positions 1and 8 being not both substituted by OH-groups simultaneously with thesubstitution of both the 3- and G-positions by SO3I-I-groups, saidproducts being in the free state weakly colored crystals, dissolvingreadily in water, and being valuable intermediate products for themanufacture of dyestuffs and pharmaceutical products.

' 2.As new products, substitution products of carbazole sulphonic acidsof the formula:

" f NH in); \on).

a V "S011 SOH s a a 'olajf on forming in the form of the sodium saltlong, weakly brown coloredneedles dissolving readily in water. 1

4. As a new product, the compound of the formula:

sgfl q/SOQI forming in the form of the sodium salt short, spindle-shapedneedles dissolving readily in water.

5. As a new product, the compound of the formula:

OaH S 0311 being in the free state weakly brown colored needles,dissolving readily in water, and being valuable intermediate productsfor the manufacture of dyestuffs and pharmaceutical products.

6. As new products the compounds of the formula:

said products being in the free state weakly colored crystals,dissolving readily in water, and being valuable intermediate productsfor the manufacture of dyestuffs and pharmaceutical products. FRIEDRICHMUTH.

ALBERT SCHMELZER.

